The invention relates to penta- and hexacoordinated ruthenium and osmium carbene catalyst, to their preparation and to their use for synthesizing polymers, for ring-closing metathesis of olefins and for isomerizing olefins.
The thermal metathesis polymerization of cycloolefins which are under ring strain, which has acquired great importance in recent times, requires appropriate catalysts. Whereas initially use was made of catalyst and cocatalystxe2x80x94see, for example U.S. Pat. No. 4,060,468 and International Patent Application WO 93/13171xe2x80x94one-component catalysts have also been disclosed [H. H. Thai et al., J. Mol. Catal. 15:245-270 (1982)]. Catalysts of particular interest for the application are so-called metal carbenes, i.e. transition metal compounds, for example ruthenium and osmium complexes, having a group xe2x95x90CRxe2x80x2Rxe2x80x3 attached to the central metal atom [WO 93/201111; S. Kanaoke et al., Macromolecules 28:4707-4713 (1995); C. Fraser et al., Polym. Prepr. 36:237-238 (1995); P. Schwab et al., Angew. Chem. 107:2179-2181 (1995)]. This type of complex is also suitable for catalysing ring closure in dienes [WO 96/04289]. The known catalysts are pentacoordinated and in addition to the group xe2x95x90CRxe2x80x2Rxe2x80x3 contain two identical tertiary phosphine groups, attached to the metal atoms, as neutral exe2x88x92 donor ligands [WO 93/20111; WO 96/04289]. Z. Wu et al., J. Amer. Chem. Soc. 1995, 117, 5503-5511 disclose on page 5 the alkanethio-substituted ruthenium carbene complex (trifluoroacetate)2(PPh3)2Ru(CHSCH2Ph). However, it is also disclosed on page 5508, left column, last sentence, that this complex is inactive for catalyzing the ROMP (=Ring Opening Metathesis Polymerization) of bicyclo[3.2.0]hept-6-ene.
The present invention is based on the object of providing further. improved catalysts for thermal metathesis polymerization. It has surprisingly been found that pentacoordinated ruthenium and osmium catalysts having a group xe2x95x90CRxe2x80x2Rxe2x80x3 (Rxe2x80x2=hydrogen and Rxe2x80x3=arylthio) attached to the central metal atom, and hexacoordinated ruthenium and osmium catalysts having the group xe2x95x90CRxe2x80x2Rxe2x80x3 in which one of the radicals Rxe2x80x2 or Rxe2x80x3 is an organic radical which is attached via a nonmetallic heteroatom of the oxygen, sulfur or nitrogen type to the carbon atom of the carbene group, are excellent catalysts for metathesis reactions and for the ring closure of dienes. By an appropriate choice of neutral and anionic ligands it is possible to exercise close control over the reactivity, for example the latency, over a wide range.
The invention provides compounds of the formula 
in which Me and Mexe2x80x2 independently of one another are ruthenium or osmium;
X Xxe2x80x2, Y and Yxe2x80x2 independently of one another are anionic ligands or X and Y and Xxe2x80x2 and Yxe2x80x2 in each case together are bisanionic ligands;
L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 independently of one another are monodentate, neutral exe2x88x92 donor ligands;
L4 is a bidentate- or, together with two of the ligands L1, L2, L2xe2x80x2, L3xe2x80x2, L5 and L5xe2x80x2, a tetradentate-neutral exe2x88x92 donor ligand;
Z is sulfur or the group 
in which Rxe2x80x2xe2x80x3 is hydrogen or a hydrocarbon radical;
Z1 and Z1xe2x80x2 independently of one another are oxygen, sulfur or the groups 
and Axe2x80x2;
R is unsubstituted or substituted arts if Z is sulfur or is a hydrocarbon radical if Z is the groups A and Axe2x80x2; and
Rxe2x80x2 and Rxe2x80x3 are a hydrocarbon radical, or an isomer of this compound;
with the exception of compounds (Ib), wherein one of L1, L2 and L3 represents carbonyl.
The invention likewise provides compounds of the formulae Ia-Ie including all cases of isomerism of the type, for example, of coordination isomerism or bond isomerism, which results from differing spatial arrangement of the ligands around the central atom, but also stereoisomers. For compounds of the formula Ia the following isomeric structures of the formulae 
are possible, in which Me, X, Y, L1, L2, Z and R are as defined above. For compounds of the formulae Ib-Ie analogous isomeric structures are possible, which are likewise provided by the present invention. The invention likewise provides sterereoisomeric compounds which result from the presence of a centre of chirality in one of the specified ligands or in a side chain. These cases of isomerism include optically pure enantiomners, diastereomers and racemic mixtures.
The terms and definitions used in the description of the present invention preferably have the following meanings:
In the compounds of the formula Ia-Ie Me and Mexe2x80x2 are preferably ruthenium
The anionic ligands X, Xxe2x80x2, Y and Yxe2x80x2 are, for example, hydride ions (Hxe2x88x92) or are derived from inorganic or organic acids, examples being halides, e.g. Fxe2x88x92, Clxe2x88x92, Brxe2x88x92 or Ixe2x88x92, fluoro complexes of the type BF4xe2x88x92, PF6xe2x88x92, SbFd6xe2x88x92 or AsF6xe2x88x92, anions of oxygen acids, alcoholates or acetylides or anions of cyclopentadlene.
The anions of oxygen acids can be, for example, sulfate, phosphate, perchlorate, perbromate, periodate, antimonata, arsenate, nitrate, carbonate, the anion of a C1-C8carboxylic acid, such as formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C1-C4alkyl, C1-C4alkoxy or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate.
Such anions are, for example, anions of oxygen acids, examples being sulfate, phosphate, perchlorate, perbromate, periodate, antimonate, arsenate, nitrate or carbonate, sulfonates, for example methylsulfonate, ethylsulfonate, propylsulfonate, butylsulfonate, trifluoromethylsulfonate (triflate), unsubstituted or C1-C4alkyl-, C1-C4alkoxy- or halo-, especially fluoro-, chloro- or bromo-substituted phenylsulfonate or benzylsulfonate, for example tosylate, mesylate, brosylate, p-methoxy- or p-ethoxyphenylsulfonate, pentafluorophenylsulfonate or 2,4,6-triisopropylsulfonate, phosphonates, for example methylphosphonate, ethylphosphonate, propylphosphonate, butylphosphonate, phenylphosphonate, p-methyl-phenylphosphonate or benzylphosphonate, carboxylates derived from a C1-C8carboxylic acid, for example formate, acetate, propionate, butyrate, benzoate, phenylacetate, mono-, di- or trichloro- or -fluoroacetate, and also C1-C12xe2x80x94, preferably C1-C6xe2x80x94 and, with particular preference, C1-C4alcoholates, which in particular are branched, being for example of the formula RxRyRzCxe2x80x94Oxe2x88x92 in which Rx is H or C1-C10alkyl, Ry is C1-C10alkyl and Rz is C1-C10alkyl or phenyl, and the sum of the carbon atoms of Rx, Ry and Rz is at least 2, preferably at least 3 and up to 10.
Other suitable anions are C1-C12xe2x80x94, preferably C1-C6xe2x80x94 and, with particular preference, C1-C4alcoholates, which in particular are branched, being for example of the formula RxRyRzCxe2x80x94Oxe2x88x92 in which Rx is H or C1-C10alkyl, Ry is C1-C10alkyl and Rz is C1-C10alkyl or phenyl, and the sum of the carbon atoms of Rx, Ry and Rz is at least 2, preferably at least 3 and up to 10.
Other suitable anions are C3-C18xe2x80x94, preferably C5-C14xe2x80x94 and, with particular preference, C5-C12acetylides, which may be of the formula Rwxe2x80x94Cxe2x89xa1Cxe2x88x92 in which Rw is C1-C16alkyl, preferably xcex1-branched C3-C12alkyl, for example of the formula RxRyRzCxe2x80x94, or is unsubstituted or mono- to tri-C1-C4alkyl or xe2x80x94C1-C4alkoxy-substituted phenyl or benzyl. Some examples are i-propyl, i- and t-butyl, phenyl, benzyl, 2-methylphenyl, 2,6-dimethylphenyl, 2-i-propylphenyl, 2-i-propyl-6-methylphenyl, 2-t-butylphenyl, 2,6-di-t-butylphenyl and 2-methyl-6t-butylphenyl acetylide.
Further anionic ligands are organic radicals having negative charges, such as C1-C12alkyl, e.g. methyl, or aralkyl, e.g. benzyl.
Particularly preferred anionic ligands are Hxe2x88x92, Fxe2x88x92, Clxe2x88x92, Brxe2x88x92, BF4xe2x88x92; PF6xe2x88x92, SbF6xe2x88x92, AsF6xe2x88x92, CF3SO3xe2x88x92, C6H5xe2x80x94SO3xe2x88x92, 4-methyl-C6H4xe2x80x94SO3xe2x88x92, 3,5-dimethyl-C6H3xe2x80x94SO3xe2x88x92, 2,4,6-trimethyl-C6H2xe2x80x94SO3xe2x88x92 and 4-CF3xe2x80x94C6H4xe2x80x94SO3xe2x88x92 and also cyclopentadienyl (Cpxe2x88x92). Clxe2x88x92 is particularly preferred.
Examples of bisanionic ligands X, Xxe2x80x2, Y and Yxe2x80x2 are the bisanions of diols, diamines and hydroxyamines, such as catechol, N,Nxe2x80x2-dimethyl-1,2-benzenediamine, 2-(methylamino)phenol, 3-(methylamino)-2-butanol and N,Nxe2x80x2-bis(1,1-dimethylethyl)-1,2-ethanediamine.
In the compounds of the formulae (Ia)-(Ie) one or two neutral ligands from the group L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 are tertiary-substituted phosphine having 3-about 40, preferably 3-30 and, with particular preference, 3-18 carbon atoms. The tertiary-substituted phosphine is preferably a compound of the formula 
in which R1, R2 and R3 independently of one another are C1-C20alkyl, C3-C12cycloalkyl, C2-C11heterocycloalkyl, C5-C12aryl, C1-C12heteroaryl or C6-C14aralkyl, where alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and aralkyl are unsubstituted or substituted by one or more substituents of the group consisting of C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, C5-C12aryl, xe2x80x94NO2, SO3xe2x88x92, ammonium and halogen; the radicals R1 and R2 together are unsubstituted or C1-C6alkyl-, C1-C6haloalkyl-, xe2x80x94NO2xe2x80x94 or C1-C6alkoxy-substituted tetra- or pentamethylene, which may be fused to 1 or 2 1,2-phenylene radicals, and R3 is as defined above.
Examples of alkyl are methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl. An example of aryl-substituted alkyl is benzyl. Examples of alkoxy are methoxy, ethoxy and the isomers of propoxy and butoxy.
Some examples of cycloalkyl are cyclobutyl, cycloheptyl, cyclooctyl and especially cyclopentyl and cyclohexyl. Examples of substituted cycloalkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis-trifluoromethyl- and tris-trifluoromethyl-substituted cyclopentyl and cyclohexyl.
Examples of aryl are phenyl and naphthyl. Examples of aryloxy are phenoxy and naphthyloxy. Examples of substituted aryl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis-trifluoromethyl- or tris-trifluoromethyl-substituted phenyl. An example of aralkyl is benzyl. Examples of substituted aralkyl are methyl-, dimethyl-, trimethyl-, methoxy-, dimethoxy-, trimethoxy-, trifluoromethyl-, bis-trifluoromethyl or tris-trifluoromethyl-substituted benzyl.
In the context of the present invention heterocycloalkyl embraces one or two and heteroaryl from one to four heteroatoms, the heteroatoms being selected from the group nitrogen, sulfur and oxygen. Some examples of heterocycloalkyl are tetrahydrofuryl, pyrrolidinyl, piperazinyl and tetrahydrothienyl. Some examples of heteroaryl are furyl, thienyl, pyrrolyl, pyridyl and pyrimidinyl.
Preference is given to compounds of the formulae Ia-Ie in which one or two ligands from the group L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 are tertiary-substituted phosphine of the formula II in which R1, R2 and R3 are identical substituents, e.g. C1-C6alkyl or phenyl. Particular preference is given, furthermore, to radicals R1, R2 and R3 which are sterically bulky, for example cyclic or branched, especially xcex1,xcex1-di-branched and very especially xcex1-branched alkyl groups.
Another group of preferred compounds is formed by those compounds of the formulae Ia-Ie in which one or two ligands from the group L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 independently of one another are tertiary-substituted phosphine (II) in which R1, R2 and R3 independently of one another are C1-C12alkyl, C5-C8cycloalkyl, C6-C12aryl or C7-C13aralkyl in which alkyl, cycloalkyl, aryl and aralkyl are unsubstituted or substituted by one or more substituents selected from the group C1-C6alkyl, C1-C6alkoxy, C1-C6haloalkyl, sulfo, trimethylamino, triethylamino, ammonium and trifluoromethyl.
Within this group particular preference is given to those phosphines (II) in which R1, R2 and R3 independently of one another are C1-C8alkyl, C5- or C6-cycloalkyl, C6-C10aryl or C7-C12aralkyl in which alkyl, cycloalkyl, aryl and aralkyl are unsubstituted or substituted by from one to three substituents selected from the group methyl, methoxy, ethyl, ethoxy and trifluoromethyl.
Particular preference is given to phosphines (II) in which R1, R2 and R3 are methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2- or 3-pentyl, 1-, 2-, 3- or 4-hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl or benzyl.
Particular preference is given to compounds (11) in which R1, R2 and R3 are methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, 1-, 2- or 3-pentyl, 1-, 2-, 3- or 4-hexyl, cyclopentyl, cyclohexyl, phenyl, naphthyl or benzyl, e.g. (i-C3H7)3P, (C5H9)3P and (C6H11)3P.
In the compounds of the formulae (Ia)-(Ie) some ligands from the group L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 are monodentate, neutral exe2x88x92 donor ligands having electron donor properties, two ligands from this group together are bidentate, neutral exe2x88x92 donor ligands and the neutral ligand from the group L4 is a bidentatexe2x80x94or, together with two ligands of the group L1, L2, L2xe2x80x2, L3xe2x80x2, L5 and L5xe2x80x2, a tetradentatexe2x80x94neutral exe2x88x92 donor ligand. Such ligands are derived from unsubstituted or substituted heteroarenes from the group consisting of furan, thiophene, pyrrole, pyridine, bis-pyridine, picolylimine, xcex3-pyran, xcex3-thiopyran, phenanthroline, pyrimidine, bis-pyrimidine, pyrazine, indole, coumarone, thionaphthene, carbazole, dibenzofuran, dibenzothiophene, pyrazole, imidazole, benzimidazole, oxazole, thiazole, bis-thiazole, isoxazole, isothiazole, quinoline, bis-quinoline, isoquinoline, bis-isoquinoline, acridine, chromene, phenazine, phenoxazine, phenothiazine, triazine, thianthrene, purine, bis-imidazole and bis-oxazole.
Examples of substituents of these groups are OH, halo, xe2x80x94C(xe2x95x90O)xe2x80x94ORs1, xe2x80x94Oxe2x80x94C(xe2x95x90O)Rs4, C(xe2x95x90O)Rs2, nitro, NH2, cyano, xe2x80x94SO3My, xe2x80x94Oxe2x80x94SO3My, xe2x80x94N(R20)xe2x80x94SO3My, xe2x80x94Nxe2x95x90Nxe2x80x94Rs2, C1-C12alkyl, C2-C12alkenyl, C1-C12alkoxy, C3-C12cycloalkyl, C3-C12cycloalkenyl, C2-C13heterocycloalkyl, C2-C13heterocycloalkenyl, C5-C12aryl, C5-C12aryloxy, C6-C14aralkyl, C6-C14aralkenyl, C1-C9heteroaryl, C2-C9heteroaryloxy, C2-C12heteroaralkyl, C3-C12heteroaralkenyl. monoamino, diamino, sulfonyl, sulfonamide, carbamide, carbamate, sulfonhydrazide, carbohydrazide, carbohydroxamic acid and aminocarbonylamide, in which My, Rs1; Rs2, Rs4 and R20 are C1-C12alkyl, C2-C12alkenyl, C3-C12cycloalkyl, C3-C12cycloalkenyl, C2-C13-heterocycloalkyl, C2-C13heterocycloalkenyl, C5-C12aryl, C5-C14aralkyl, C6-C1aralkenyl, C1-C9-heteroaryl, C2-C12heteroaralkyl or C3-C12heteroaralkenyl and Rs1, Rs2, Rs4 and R20 are otherwise hydrogen, and alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, aralkyl, aralkenyl, heteroaryl, heteroaralkyl or heteroaralkenyl are in turn unsubstituted or substituted by one of the specified substituents; and y is 1 and M is a monovalent metal or y is 1/2 and M is a bivalent metal cation.
In the context of the description of the present invention the terms metal and cations mean an alkali metal, for example Li, Na or K, an alkaline earth metal, for example Mg, Ca or Sr, or Mn, Fe, Zn or Ag, and the corresponding cations. Salts with lithium, sodium and potassium cations are preferred.
Monoamino, diamino, carbamide, carbamate, carbohydrazide, sulfonamide, sulfohydrazide and aminocarbonylamide correspond preferably to a group R8C(xe2x95x90O)(NH)pN(R9)xe2x80x94, xe2x80x94C(xe2x95x90O)(NH)pNR8R9, R8Oxe2x80x94C(xe2x95x90O)(NH)pN(R9)xe2x80x94, R8R40Nxe2x80x94C(xe2x95x90O)(NH)pN(R9)xe2x80x94, xe2x80x94OC(xe2x95x90O)(NH)pNR8R9, xe2x80x94N(R40)xe2x80x94C(xe2x95x90O)(NH)pNR8R9, R8S(O)2(NH)pN(R9)xe2x80x94; xe2x80x94S(O)2(NH)pNR8R9; R8R40NS(O)2N(R9)xe2x80x94 or xe2x80x94NR40S(O)2NR8R9, in which R8, R9 and R40 independently of one another are hydrogen or substituents from the group OH, C1-C12alkyl, C2-C12alkenyl, C3-C12-cycloalkyl, C3-C12cycloalkenyl, C2-C13heterocycloalkyl, C2-C13heterocycloalkenyl, C5-C12aryl, C1-C9heteroaryl, C6-C14aralkyl, C7-C14aralkenyl with C2-C6alkenylene and C5-C12aryl, C6-C15-heteroaralkyl, C5-C14heteroaralkenyl and di-C6-C10aryl-C1-C6alkyl, and in which in the group R8xe2x80x2R9xe2x80x2N the substituents R8xe2x80x2 and R9xe2x80x2 independently of one another are hydrogen or substituents from the group OH, SO3My, OSO3My, C1-C12alkyl, C3-C12cycloalkyl, C2-C11heterocycloalkyl, C6-C10aryl, C5-C9heteroaryl, C7-C11aralkyl, C6-C10heteroaralkyl, C8-C16aralkenyl with C2-C6-alkenylene and C6-C10aryl and di-C6-C10aryl-C1-C6alkyl, which are unsubstituted or substituted by one or more substituents from the group OH, halo, xe2x80x94C(xe2x95x90O)xe2x80x94ORs1, xe2x80x94Oxe2x80x94C(xe2x95x90O)Rs4, xe2x80x94C(xe2x95x90O)Rs2, nitro, NH2, cyano, xe2x80x94SO3My, xe2x80x94Oxe2x80x94SO3My, xe2x80x94N(R20)xe2x80x94SO3My, xe2x80x94Nxe2x95x90Nxe2x80x94Rs2, C1-C12alkyl, C2-C12alkenyl, C1-C12alkoxy, C3-C12cycloalkyl, C3-C12cycloalkenyl, C2-C13heterocycloalkyl, C2-C13-heterocycloalkenyl, C5-C12aryl, C5-C12aryloxy, C6-C14aralkyl, C6-C14aralkoxy, C7-C14aralkenyl, C1-C9heteroaryl, C2-C9heteroaryloxy, C2-C12heteroaralkyl, C3-C12heteroaralkenyl, monoamino, diamino, sulfonyl, sulfonamide, carbamide, carbamate, sulfohydrazide, carbohydrazide, the carbohydramic acid radical and aminocarbonylamide radical, in which My, Rs1, Rs2, Rs4 and R20 are C1-C12alkyl, C2-C12alkenyl, C3-C12cycloalkyl, C3-C12cycloalkenyl, C2-C13-heterocycloalkyl, C2-C11heterocycloalkenyl, C6-C12aryl, C6-C13aralkyl, C6-C13aralkenyl, C1-C9-heteroaryl, C2-C12heteroaralkyl or C3-C12heteroaralkenyl and Rs1, Rs2, Rs4 and R20 are otherwise hydrogen, and alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, aralkyl, aralkenyl, heteroaryl, heteroaralkyl or heteroaralkenyl in turn are unsubstituted or substituted by one of the specified substituents; and y is 1 and M is a monovalent metal or y is 1/2 and M is a divalent metal; or R8 and R9 or R8xe2x80x2 and R9xe2x80x2 or R8 and R40 in the case of xe2x80x94NR8R9 or xe2x80x94NR8xe2x80x2R9xe2x80x2 or R8R40Nxe2x80x94 together are tetramethylene, pentamethylene, xe2x80x94(CH2)2xe2x80x94Oxe2x80x94(CH2)2xe2x80x94, xe2x80x94(CH2)2xe2x80x94Sxe2x80x94(CH2)2xe2x80x94 or xe2x80x94(CH2)2xe2x80x94NR7xe2x80x94(CH2)2xe2x80x94, and R7 is hydrogen, C1-C6alkyl, C6-C13aralkyl, xe2x80x94C(xe2x95x90O)Rs2 or sulfonyl.
The sulfonyl substituent corresponds, for example, to the formula R10xe2x80x94SO2xe2x80x94 in which R10 is C1-C12alkyl, C3-C12cycloalkyl, C2-C11heterocycloalkyl, C5-C12aryl, C1-C9heteroaryl, C6-C13-aralkyl or C2-C13heteroaralkyl which is unsubstituted or substituted by one or more substituents from the group OH, halo, xe2x80x94C(xe2x95x90O)xe2x80x94ORs1, xe2x80x94Oxe2x80x94C(xe2x95x90O)Rs4, xe2x80x94C(xe2x95x90O)Rs2, nitro, NH2, cyano, xe2x80x94SO3My, xe2x80x94Oxe2x80x94SO3My, xe2x80x94N(R20)xe2x80x94SO3My, xe2x80x94Nxe2x95x90Nxe2x80x94Rs2, C1-C12alkyl, C2-C12alkenyl, C1-C12-alkoxy, C3-C12cycloalkyl, C3-C12cycloalkenyl, C2xe2x80x94C13heterocycloalkyl, C2xe2x80x94C13-heterocycloalkenyl, C5-C12aryl, C5-C12aryloxy, C6-C13aralkyl, C6-C13aralkoxy, C6-C13-aralkenyl, C1-C9heteroaryl, C2-C9heteroaryloxy, C2-C12heteroaralkyl, C3-C12heteroaralkenyl, monoamino, diamino, sulfonyl, sulfonamide, carbamide, carbamate, sulfohydrazide, carbohydrazide, the carbohydroxamic acid radical and aminocarbonylamide radical, in which My, Rs1, Rs2, Rs4 and R20 are C1-C12alkyl, C2-C12alkenyl, C3-C12cycloalkyl, C3-C12cycloalkenyl, C2-C13-heterocycloalkyl, C2-C13heterocycloalkenyl, C5-C12aryl, C6-C13aralkyl, C6-C13aralkenyl, C1-C9-heteroaryl, C2-C12heteroaralkyl or C3-C12heteroaralkenyl and Rs1, Rs2, Rs4 and R20 are otherwise hydrogen, and alkyl, alkenyl, cycloalkyl, cycloalkenyl, heterocycloalkyl, heterocycloalkenyl, aryl, aralkyl, aralkenyl, heteroaryl, heteroaralkyl or heteroaralkenyl in turn are unsubstituted or substituted by one of the specified substituents; and y is 1 and M is a monovalent metal or y is 1/2 and M is a bivalent metal cation.
Preferred monodentate and bidentate exe2x88x92 donor ligands are derived, for example, from heteroarenes of the group: 
A preferred group is formed by those compounds of the formulae Ia-Ie in which one or two ligands from the group L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 in each case independently of one another are monodentate pyridine which is unsubstituted or substituted by one or more substituents from the group C1-C12alkyl C2-C11heterocycloalkyl, C5-C9heteroaryl, monoamino, diamino and xe2x80x94C(xe2x95x90O)H. Examples of such ligands are 
Another preferred group of compounds is formed by compounds of the formulae Ia-Ie, in which two of the ligands L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 together are bidentate bis-pyridine, phenanthrolinyl, bis-thiazolyl, bis-pyrimidine or picolylimine, which are unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, C6-C10aryl and cyano where the substituents alkyl and aryl in turn are unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, nitro, monoamino, diamino and nitro- or secondary amino-substituted xe2x80x94Nxe2x95x90Nxe2x80x94C6-C10aryl. Examples of such ligands are 
Another preferred group of compounds is formed by compounds of the formulae Ia-Ie, in which L4 is bidentate bipyridine or together with two of the ligands L1, L2, L2xe2x80x2, L3, L5 and L5xe2x80x2 is tetradentate bipyrimidine, which are unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, C2-C11heterocycloalkyl, C5-C9heteroaryl, monoamino, diamino and xe2x80x94C(xe2x95x90O)H. One example of a tetradentate ligand of this type is 
A further preferred group of compounds is formed by compounds of the formulae Ia-Ie, in which two of the ligands L1, L2, L2xe2x80x2, L3xe2x80x2, L5 and L5xe2x80x2 together, or L4, is bidentate pyridine which is unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, C2-C11heterocycloalkyl, C5-C9heteroaryl, monoamino, diamino and xe2x80x94C(xe2x95x90O)H. One example of a ligand of this type is 
In compounds of the formula Ia Z is sulfur or the groups 
in which Rxe2x80x2xe2x80x3 is hydrogen or a hydrocarbon radical. The term hydrocarbon radical for Rxe2x80x2xe2x80x3 embraces the definitions given earlier for R1, R2 and R3 under compounds (II), especially the aliphatic, cycloaliphatic or cycloaliphatic-aliphatic radicals, carbocyclic aryl radicals or aryl-aliphatic radicals specified there with the further substituents which were likewise mentioned, and also the heterocyclic groups defined under the ligands of the group L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 with the further substituents specified there. Provided that Z has the definitions of A or Axe2x80x2, R is a hydrocarbon radical having the definitions specified for Rxe2x80x2xe2x80x3.
If Z in compounds of the formula Ia is sulfur, R is aryl, for example unsubstituted phenyl or phenyl which is substituted by one or more substituents from the group consisting of C1-C6-alkyl, C1-C6alkoxy, carboxyl, C1-C6alkoxycarbonyl, C1-C6haloalkyl, nitro, sulfo, ammonium and halo.
In compounds of the formulae Ia Z can also be the groups A and Axe2x80x2, in which Rxe2x80x2xe2x80x3 is preferably hydrogen, C1-C20alkyl, C3-C8cycloalkyl, C3-C7heterocycloalkyl, C5-C12aryl or C1-C9heteroaryl, in which alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by one or more substituents from the group C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, carboxyl, C1-C6alkoxycarbonyl, C5-C12aryl, C5-C12aryloxy, xe2x80x94NO2 and halo. R in this case is a hydrocarbon radical having the definitions specified for Rxe2x80x2xe2x80x3.
In compounds of the formulae Ib-Ie Z1 and Z1xe2x80x2 independently of one another are oxygen, sulfur or the groups A and Axe2x80x2 having the specified definitions.
If Z1 and Z1xe2x80x2 in compounds of the formulae Ib-Ie have these definitions, Rxe2x80x2 and Rxe2x80x3 are hydrocarbon radicals having the definitions specified for R under A and Axe2x80x2, especially the aliphatic, cycloaliphatic or cycloatiphatic-aliphatic radicals, carbocyclic aryl radicals or arylaliphatic radicals specified there with the further substituents specified there. In dimeric compounds of the formulae Ic, Id and Ie, R and R can also be bridged with one another by way, for example, of C2-C10alkylene groups which can in turn be substituted by functional groups, e.g. halo, hydroxyl, alkoxy, etc.
In compounds of the formulae Ib-Ie Rxe2x80x2 and Rxe2x80x3 are preferably C1-C20alkyl, C3-C8cycloalkyl, C3-C7heterocycloalkyl, C5-C12aryl or C1-C9heteroaryl, in which alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by one or more substituents from the group C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, carboxyl, C1-C6alkoxycarbonyl, C5-C12aryl, C5-C12aryloxy, xe2x80x94NO2 and halo. If Z1 and Z1xe2x80x2 in compounds of the formulae Ib-Ie are the groups A and Axe2x80x2, Rxe2x80x2xe2x80x3 therein has the preferred definitions specified for Rxe2x80x2 and Rxe2x80x3.
Furthermore, if Z, Z1 or Z1xe2x80x2 in compounds of the formulae Ia-Ie has the definition of the groups A and Axe2x80x2, the substituents Rxe2x80x2xe2x80x3 and R or Rxe2x80x2 and Rxe2x80x3, including phosphorus or preferably nitrogen of the group Z, can be joined to one another to form a heterocycle which can be unsaturated, partly saturated or fully saturated and can carry further substituents, e.g. alkyl, alkoxy, halo, hydroxyl or oxo. This case is illustrated by the following example: 
The invention preferably provides compounds of the formulae 
according to claim 1
in which L2, L2xe2x80x2, L3, L3xe2x80x2 and L5 independently of one another are monodentate, neutral exe2x88x92 donor ligands; L4 is a bidentatexe2x80x94or, together with two of the ligands L2, L2xe2x80x2, L3xe2x80x2 and L5, a tetradentatexe2x80x94neutral exe2x88x92 donor ligand; R1, R2 and p3 independently of one another are C1-C20alkyl, C3-C12cycloalkyl, C2-C11heterocycloalkyl, C5-C12aryl, C1-C9heteroaryl or C6-C13aralkyl, and alkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and aralkyl are unsubstituted or substituted by one or more substituents from the group consisting of C1-C6alkyl, C1-C6alkoxy, carboxyl, C1-C6alkoxycarbonyl, C1-C6haloalkyl, C5-C12aryl, C5-C12-aryloxy, xe2x80x94NO2, sulfo, ammonium and halo; the radicals R1 and R2 together are unsubstituted or C1-C6alkyl-, C1-C6haloalkyl-, xe2x80x94NO2xe2x80x94 or C1-C6alkoxy-substituted tetra- or pentamethylene, or are unsubstituted or C1-C6alkyl-, C1-C6haloakyl-, xe2x80x94NO2 or C1-C6alkoxy-substituted tetra- or pentamethylene which are fused to one or two 1,2-phenylenes, and R3 is as defined;
Z is sulfur or the group 
in which Rxe2x80x2xe2x80x3 is hydrogen or a hydrocarbon radical from the group C1-C20alkyl, C3-C8-cycloalkyl, C3-C8heterocycloalkyl, C5-C12aryl, C1-C9heteroaryl and C6-C13aralkyl, in which alkyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted by C1-C6alkyl, C1-C6haloalkyl, C1-C6alkoxy, carboxyl, C1-C6alkoxycarbonyl, C5-C12aryl, C5-C12-aryloxy, xe2x80x94NO2 or halo;
Z1 and Z1xe2x80x2 independently of one another are oxygen, sulfur or the groups 
xe2x80x83and Axe2x80x2 with the definitions specified for Rxe2x80x2xe2x80x3;
R is substituted or substituted aryl if is sulfur or is a hydrocarbon radical having the definitions specified for Rxe2x80x2xe2x80x3 if Z has the definition of the groups A and Axe2x80x2; and Rxe2x80x2 and Rxe2x80x2xe2x80x3 are a hydrocarbon radical having the definitions specified for Rxe2x80x2xe2x80x3, or an isomer of this compound;
with the exception of compounds (Ixe2x80x2b), wherein one of L2 and L3 represents carbonyl.
The invention preferably provides a selected group of compounds of the formulae Ixe2x80x2a-Ixe2x80x2e, in which L2, L2xe2x80x2, L3 and L3xe2x80x2 independently of one another are pyridyl which is unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, C3-C11heterocycloalkyl, C1-C9heteroaryl, monoamino, diamino and xe2x80x94C(xe2x95x90O)H; or two ligands L2, L2xe2x80x2, L3 and L3xe2x80x2 together are bis-pyridine, phenanthroline, bis-thiazole, bis-pyrimidine, bis-quinoline or picolylimine which are unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, C6-C10aryl and cyano, where the substituents alkyl and aryl are in turn unsubstituted or substituted by one or more substituents from the group C1-C12alkyl, nitro, monoamino, diamino and nitro- or diamino-substituted xe2x80x94Nxe2x95x90Nxe2x80x94C6-C10aryl; L4 is bis-pyridine or bis-pyrimidine:
R1, R2 and R3 are isopropyl, sec-butyl, cyclopentyl or cyclohexyl;
Z is sulfur or groups A and Axe2x80x2, in which Rxe2x80x2xe2x80x3 is hydrogen, C1-C4alkyl, phenyl or C1-C4-alkyl-substituted phenyl;
Z1 and Z1xe2x80x2 independently of one another are oxygen, sulfur or the groups A and Axe2x80x2 with the definitions specified for Rxe2x80x2xe2x80x3;
R is phenyl if Z is sulfur or is C1-C4alkyl, phenyl or C1-C4alkyl-substituted phenyl if Z has the definition of the groups A and Axe2x80x2; and
Rxe2x80x2 and Rxe2x80x3 are C1-C4alkyl, phenyl or C1-C4alkyl-substituted phenyl, and isomers of these compounds.
The invention likewise preferably provides the specified compounds of the formulae Ia-Ie, in which Z and/or Z1 or Z1xe2x80x2 has the definition of the groups A and Axe2x80x2, the substituents Rxe2x80x2xe2x80x3 and R and/or Rxe2x80x2 and Rxe2x80x3 including nitrogen from the group Z and/or Z1 or Z1xe2x80x2 are joined to one another to form a heterocycle which is unsaturated, partly saturated or fully saturated and can carry further substituents, for example alkyl, alkoxy, halo, hydroxyl or oxo.
The invention likewise preferably provides the compounds specified in the Examples, e.g. dichlorobis[tricyclohexylphosphino]phenylthiomethinoruthenium or dichlorobis[tricyclohexylphosphino]-1-(2-oxopyrrolidino)methinoruthenium and isomers of these compounds.
The invention likewise provides a process for preparing compounds of the formulae Ia-Ie according claim 1, which comprises replacing the ligand L2 or L3 in a compound of the formula 
in which Ra is an eliminable leaving group of the substrate and X, Y, L1, L2 and L3 are as defined for the formulae Ia and Ib with a vinyl ether, vinyl thioether, vinylamine or vinylphosphine of the formula 
in which Rb is an eliminable leaving group of the reagent and Z, Z1, R and Rxe2x80x2 are as defined for formulae Ia and Ib, and, if desired, for the preparation of dimeric compounds of the formulae Ic, Id and Ie, replacing the ligand L2 or L3 by a bidentate or tetradentate ligand L4, and/or substituting the groups X, Xxe2x80x2, Y and Yxe2x80x2 and also L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L5 and L5xe2x80x2 in an obtainable compound of the formulae Ia-Ie.
The process of the invention is advantageously conducted in such a way that the compounds of the formulae IIIa and IIIb are dissolved in a solvent and then the desired vinyl ether, vinyl thioether, vinylamine or vinylphosphine (IVa) or (IVb) is added. The mass ratio of compounds (IIIa) and (IIIb) to compounds (IVa) and (IVb) is generally within the range from 1:1 to 1:100, preference being given to a ratio in the range from 1:1 to 1:5. The reaction takes place within a temperature range from xe2x88x9280xc2x0 C. to 150xc2x0 C., preferably from 0xc2x0 C. to 100xc2x0 C. and, with particular preference, at from room temperature to 50xc2x0 C.
The invention likewise provides a composition comprising
(xcex1) dicyclopentadiene or another strained cycloolefin, or dicyclopentadiene in a mixture with another strained cycloolefin, and
(xcex2) a catalytic amount of at least one compound of the formulae Ia-Ie, in which Me and Mexe2x80x2 independently of one another are ruthenium or osmium and X, Xxe2x80x2, Y, Yxe2x80x2, L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L4, L5 and L5xe2x80x2, Z, Z1 Z1xe2x80x2, R, Rxe2x80x2 and Rxe2x80x3 are as defined, and isomers of these compounds and, if desired, further additives for polymers.
Dicyclopentadiene is the dimer of cyclopentadiene, which is known and commercially available and has the formula 
it is known that, together with further cyclopentadiene, dicyclopentadiene forms so-called Diels-Alder adducts and hence forms oligomers which can likewise be used. In accordance with the invention the composition may comprise pure dicyclopentadiene, oligomers of dicyclopentadiene or mixtures thereof. The oligomers are of the formula 
in which p is from 1 to 100, preferably from 1 to 50, with particular preference from 1 to 20 and, with especial preference, from 1 to 10.
The cycloolefins known as strained cycloolefins, which may be present as comonomers in the composition of the invention, are known.
The cyclic olefins can be monocyclic or polycyclic, fused and/or bridged ring systems, which have, for example, from two to four rings and which are unsubstituted or substituted and can contain heteroatoms such as O, S, N or Si, for example, in one or more rings and/or can contain fused aromatic or heteroaromatic rings, such as o-phenylene, o-naphthylene, o-pyridinylene or o-pyrimidinylene. The individual cyclic rings include 3 to 16, preferably 3 to 12 and, with particular preference, 3 to 8 ring members. The cyclic olefins may contain further nonaromatic double bonds, preferably from 2 to 4 such additional double bonds depending on ring size. The ring substituents involved are those which are inert; in other words, those which do not impair the chemical stability of the ruthenium and osmium compounds. The cycloolefins are strained rings or ring systems.
If the cyclic olefins contain more than one double bond, for example 2 to 4 double bonds, then depending on the reaction conditions, on the chosen monomer and on the amount of catalyst it is also possible for crosslinked polymers to form.
Fused-on alicyclic rings contain preferably 3 to 8, more preferably 4 to 7 and, with particular preference, 5 or 6 ring carbon atoms.
The cyclic olefins which are present in the composition and which may be polymerized with the aid of the catalysts of the invention are known and are described, for example, in WO 96/20235.
The comonomeric cycloolefins can be present in an amount of from 0.01 to 99% by weight, preferably from 0.1 to 95% by weight, with particular preference from 1 to 90% by weight and, with especial preference, from 5 to 80% by weight, based on the monomers present in the composition. Very particular preference is given to norbornene as comonomer in amounts, for example, of from 20 to 60% by weight.
The dienes which are present in the composition and which can be ring-closed with the aid of the catalysts of the invention are described, for example, in Miller et al. [Miller, S. J., Blackwell, H. E., Grubbs, R. H., J. Am. Chem. Soc. 118:9606-9614 (1996)] or in Grubbs et al. [Grubbs, R. H., Miller, S. J., Fu, G. C., Acc. Chem. Res. 28:446-452 (1995)].
The catalysts of the invention can also be used for breaking down unsaturated polymers or for isomerizing double bonds, as has already been described for ruthenium catalysts in McGrath and Grubbs [McGrath, D. V., Grubbs, R. H., Organometallics 13:224 (1994)].
The composition of the invention can comprise inert solvents. One particular advantage is that in the case of liquid monomers metathesis polymerization can be carried out without the use of a solvent. A further advantage is that the polymerization can even be carried out in water, polar and protic solvents or water/solvent mixtures. In such cases it is of advantage, in the context of the present invention, to use a surfactant.
Examples of suitable inert solvents are protic polar and aprotic solvents, which can be used alone or in mixtures of at least two solvents. Examples are ethers (dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol monomethyl or dimethyl ether, ethylene glycol monoethyl or diethyl ether, diethylene glycol diethyl ether, triethylene glycol dimethyl ether), halogenated hydrocarbons, etc.
Compositions of the invention comprising a DCPD are insensitive to oxygen and moisture, which permits storage and reaction without an inert gas.
In the context of the present invention, catalytic amounts denote preferably an amount from 0.001 to 20 mol-%, with particular preference from 0.01 to 15 mol-% and, with very particular preference, from 0.01 to 10 mol-%, based on the amount of monomer. On the basis of the high thermocatalytic activity, very particular preference is given to amounts from 0.001 to 2 mol-%.
The composition of the invention which is used for the polymerization can be prepared directly prior to polymerization or can be used as a preformulated mixture, since the catalysts used are of particularly high stability. The mixture may even be stored for a prolonged period prior to polymerization, as a ready-to-use formulation, which is of advantage for large-scale industrial use.
The composition of the invention can comprise additives suitable for polymers, which additives are preferably used as formulating auxiliaries to improve the chemical and physical properties. The auxiliaries can be present in surprisingly high proportions without adversely affecting the polymerization; for example, in amounts of up to 70% by weight, preferably from 1 to 70% by weight, more preferably from 5 to 60% by weight, with particular preference from 10 to 50% by weight and with especial preference from 10 to 40% by weight, based on the composition. Such auxiliaries have been disclosed in large numbers and are set out by way of example in the following list of auxiliaries:
1.1. Alkylated Monophenols,
for example 2,6-di-tert-butyl-4-methylphenol, 2-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di-tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2-(xcex1-methylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, linear or sidechain-branched nonylphenols; such as 2,6-dinonyl-4-methylphenol, 2,4-dimethyl-6-(1xe2x80x2-methylundec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methylheptadec-1xe2x80x2-yl)phenol, 2,4-dimethyl-6-(1xe2x80x2-methyltridec-1xe2x80x2-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols,
for example 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4-nonylphenol.
1.3. Hydroquinones and Alkylated Hydroquinones,
for example 2,6-di-tert-butyl-4-methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tert-butylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.
1.4. Tocopherols,
for example xcex1-tocopherol, xcex2-tocopherol, xcex3-tocopherol, xcex4-tocopherol and mixtures thereof (vitamin E).
1.5. Hydroxylated Thiodiphenyl Ethers,
for example 2,2xe2x80x2-thiobis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-thiobis(4-octylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-3-methylphenol), 4,4xe2x80x2-thiobis(6-tert-butyl-2-methylphenol), 4,4xe2x80x2-thiobis(3,6-di-sec-amylphenol), 4,4xe2x80x2-bis(2,6-dimethyl-4-hydroxyphenyl) disulfide.
1.6. Alkylidenebisphenols,
for example 2,2xe2x80x2-methylenebis(6-tert-butyl-4-methylphenol), 2,2xe2x80x2-methylenebis(6-tert-butylethylphenol), 2,2xe2x80x2-methylenebis[4-methyl-6-(xcex1-methylcyclohexyl)phenol], 2,2xe2x80x2-methylenebis(4-methyl-6-cyclohexylphenol), 2,2xe2x80x2-methylenebis(6-nonyl-4-methylphenol), 2,2xe2x80x2-methylenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(4,6-di-tert-butylphenol), 2,2xe2x80x2-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2xe2x80x2-methylenebis[6-(xcex1-methylbenzy)-4-nonylphenol], 2,2xe2x80x2-methylenebis[6-(xcex1,xcex1-dimethylbenzyl)-4-nonylphenol], 4,4xe2x80x2-methylenebis(2,6-di-tert-butylphenol), 4,4xe2x80x2-methylenebis(6-tert-butyl-2-methylphenol), 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3-tert-butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane, ethylene glycol bis[3,3-bis(3xe2x80x2-tert-butyl-4xe2x80x2-hydroxyphenyl)butyrate], bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate, 1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane, 2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.
1.7. O-, N- and S-benzyl Compounds,
for example 3,5,3xe2x80x2,5xe2x80x2-tetra-tert-butyl-4,4xe2x80x2-dihydroxydibenzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate, bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide, isooctyl 3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated Malonates,
for example dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate, dioctadecyl 2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate, didodecyl mercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, di-[4-(1,1,3,3-tetramethylbutyl)phenyl] 2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.
1.9. Aromatic Hydroxybenzyl Compounds,
for example 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.
1.10. Triazine Compounds,
for example 2,4-bisoctylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexahydro-1,3,5-triazine, 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1.11. Benzylphosphonates,
for example dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1.12. Acylaminophenols,
for example 4-hydroxylauranilide, 4-hydroxystearanilide, octyl N-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1.13. Esters of xcex2-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Acid
with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.14. Esters of xcex2-(5-Tert-butyl-4-hydroxy-3-methylphenyl)propionic Acid
with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.15. Esters of xcex2-(3,5-Dicyclohexyl-4-hydroxyphenyl)propionic Acid
with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.16. Esters of 3,5-Di-tert-butyl-4-hydroxyphenylacetic Acid
with mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,Nxe2x80x2-bis(hydroxyethyl)oxalamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.
1.17. Amides of xcex2-(3,5-Di-tert-butyl-4-hydroxyphenyl)propionic Acid,
e.g. N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamide, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazide, N,Nxe2x80x2-bis[2-(3-[3,5-di-tert-butyl-4-hydroxyphenyl]propionyloxy)ethyl]oxamide (Naugard(copyright) XL-1 from Uniroyal).
1.18. Ascorbic Acid (vitamin C).
1.19. Aminic Antioxidants,
for example N,Nxe2x80x2-diisopropyl-p-phenylenediamine, N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, N,Nxe2x80x2-bis(1,4-dimethyl-pentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-ethyl-3-methyl-pentyl)-p-phenylenediamine, N,Nxe2x80x2-bis(1-methylheptyl)-p-phenylenediamine, N,Nxe2x80x2-dicyclohexyl-p-phenylenediamine, N,Nxe2x80x2-diphenyl-p-phenylenediamine, N,Nxe2x80x2-di-(2-naphthyl)-p-phenylenediamine, N-isopropyl-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-(1-methylheptyl)-Nxe2x80x2-phenyl-p-phenylenediamine, N-cyclohexyl-Nxe2x80x2-phenyl-p-phenylenediamine, 4-(p-toluenesulfonamido)diphenylamine, N,Nxe2x80x2-dimethyl-N,Nxe2x80x2-di-sec-butyl-p-phenylenediamine, diphenylamine, N-allyldiphenylamine, 4-isopropoxydiphenylamine, N-phenyl-1-naphthylamine, N-(4-tert-octylphenyl)-1-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,pxe2x80x2-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4-butyrylaminophenol, 4-nonanoylaminophenol, 4-dodecanoylaminophenol, 4-octadecanoylaminophenol, di-(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4-dimethylaminomethylphenol, 2,4xe2x80x2-diaminodiphenylmethane, 4,4xe2x80x2-diaminodiphenylmethane, N,N,Nxe2x80x2,Nxe2x80x2-tetramethyl-4,4xe2x80x2-diamino-diphenylmethane, 1,2-di[(2-methylphenyl)amino]ethane, 1,2-di(phenylamino)propane, (o-tolyl)biguanide, di-[4-(1xe2x80x2,3xe2x80x2-dimethylbutyl)phenyl]amine, tert-octylated N-phenyl-1-naphthylamine, a mixture of mono- and dialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamines, mixtures of mono- and dialkylated tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert-octyl-phenothiazines, a mixture of mono- and dialkylated tert-octyl-phenothiazines, N-allylphenothiazine, N,N,Nxe2x80x2,Nxe2x80x2-tetraphenyl-1,4-diaminobut-2-ene, N,N-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine, bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, 2,2,6,6-tetramethylpiperidin-4-one and 2,2,6,6-tetramethylpiperidin-4-ol.
2.1. 2-(2xe2x80x2-Hydroxyphenyl)benzotriazoles,
for example 2-(2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphehyl)benzotriazole, 2-(5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotnazole, 2-(2xe2x80x2-hydroxy-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-butyl-2xe2x80x2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-sec-butyl-5xe2x80x2-tert-butyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(2xe2x80x2-hydroxy-4xe2x80x2-octoxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-di-tert-amyl-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2,5xe2x80x2-bis(xcex1,xcex1-dimethylbenzyl)-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)-5-chlorobenzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-methoxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-5xe2x80x2-[2-(2-ethylhexyloxy)carbonylethyl]-2xe2x80x2-hydroxyphenyl)benzotriazole, 2-(3xe2x80x2-dodecyl-2xe2x80x2-hydroxy-5xe2x80x2-methylphenyl)benzotriazole, 2-(3xe2x80x2-tert-butyl-2xe2x80x2-hydroxy-5xe2x80x2-(2-isooctyloxycarbonylethyl)phenylbenzotriazole, 2,2xe2x80x2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol]; the transesterification product of 2-[3xe2x80x2-tert-butyl-5xe2x80x2-(2-methoxycarbonylethyl)-2xe2x80x2-hydroxyphenyl]benzotriazole with polyethylene glycol 300;
[Rxe2x80x94CH2CH2xe2x80x94COOxe2x80x94CH2CH2"Brketclosest"2 where R=3xe2x80x2-tert-butyl-4xe2x80x2-hydroxy-5xe2x80x2-2H-benzotriazol-2-yl-phenyl; 2-[2xe2x80x2-hydroxy-3xe2x80x2-(xcex1,xcex1-dimethylbenzyl)-5xe2x80x2-(1,1,3,3-tetramethylbutyl)phenyl]benzotriazole; 2-[2xe2x80x2-hydroxy-3xe2x80x2-(1,1,3,3-tetramethylbutyl)-5xe2x80x2-(xcex1,xcex1-dimethylbenzyl)phenyl]benzotriazole.
2.2. 2-Hydroxybenzophenones,
for example the 4-hydroxy, 4-methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2xe2x80x2,4xe2x80x2-trihydroxy and 2xe2x80x2-hydroxy-4,4xe2x80x2-dimethoxy derivative.
2.3. Esters of Substituted or Unsubstituted Benzoic Acids,
for example 4-tert-butyl-phenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert-butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.
2.4. Acrylates,
for example ethyl xcex1-cyano-xcex2,xcex2-diphenylacrylate or isooctyl xcex1-cyano-xcex2,xcex2-diphenylacrylate, methyl xcex1-carbomethoxycinnamate, methyl xcex1-cyano-xcex2-methyl-p-methoxy-cinnamate or butyl xcex1-cyano-xcex2-methyl-p-methoxycinnamate, methyl xcex1-carbomethoxy-p-methoxycinnamate and N-xcex2-carbomethoxy-xcex2-cyanovinyl)-2-methylindoline.
2.5. Nickel Compounds,
for example nickel complexes of 2,2xe2x80x2-thiobis[4-(1,1,3,3-tetramethylbutyl)phenol], such as the 1:1 or 1:2 complex, with or without additional ligands such as n-butylamine, triethanolamine or N-cyclohexyldiethanolamine, nickel dibutyldithiocarbamate, nickel salts of monoalkyl esters, such as of the methyl or ethyl ester, of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecyl ketoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additional ligands.
2.6. Sterically Hindered Amines,
for example bis(2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate, bis(1,2,2,6,6-pentamethylpiperidyl)n-butyl-3,5-di-tert-butyl-4-hydroxybenzylmalonate, the condensate of 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the linear or cyclic, condensates of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine, tris(2,2,6,6-tetramethyl-4-piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetraoate, 1,1xe2x80x2-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6-tetramethylpiperidine, 4-stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the linear or cyclic condensates of N,Nxe2x80x2-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4-morpholino-2,6-dichloro-1,3,5-triazine, the condensate of 2-chloro-4,6-di(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazine and 1,2-bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazine and 1,2-bis-(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione, 3-dodecyl-1-(2,2,6,6-tetramethyl-4-piperidyl)pyrrolidine-2,5-dione, 3-dodecyl-1-(1,2,2,6,6-pentamethyl-4-piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxy- and 4-stearyloxy-2,2,6,6-tetramethylpiperidine, the condensate of N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine and 4-cyclohexylamino-2,6-dichloro-1,3,5-triazine, the condensate of 1,2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro-1,3,5-triazine and also 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimide, N-(1,2,2,6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimide, 2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane, the reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane and epichlorohydrine, 1,1-bis(1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyl)-2-(4-methoxyphenyl)ether, N,Nxe2x80x2-bisformyl-N,Nxe2x80x2-bis(2,2,6,6-tetramethyl-4-piperidyl)-hexamethylenediamine, the diester of 4-methoxymethylenemalonic acid with 1,2,2,6,6-pentamethyl-4-hydroxypiperidine, poly[methylpropyl-3-oxy-4-(2,2,6,6-tetramethyl-4-piperidyl)]siloxane, the reaction product of maleic anhydride-xcex1-olefin copolymer and 2,2,6,6-tetramethyl-4-aminopiperidine or 1,2,2,6,6-pentamethyl-4-aminopiperidine.
2.7. Oxalamides,
for example 4,4xe2x80x2-dioctyloxyoxanilide, 2,2xe2x80x2-diethoxy-oxanilide, 2,2xe2x80x2-dioctyloxy-5,5xe2x80x2-di-tert-butyloxanilide, 2,2xe2x80x2-didodecyloxy-5,5xe2x80x2-di-tert-butyloxanilide, 2-ethoxy-2xe2x80x2-ethyloxanilide, N,Nxe2x80x2-bis(3-dimethylaminopropyl)oxalamide, 2-ethoxy-5-tert-butyl-2xe2x80x2-ethyloxanilide and its mixture with 2-ethoxy-2xe2x80x2-ethyl-5,4xe2x80x2-di-tert-butyloxanilide and mixtures of o- and p-methoxy- and of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxyphenyl)-1,3,5-triazines,
for example 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)phenyl]4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyl]-1,3,5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine, 2-{2-hydroxy-4-[3-(2-ethylhexyl-1-oxy)-2-hydroxypropyloxy]phenyl}-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine.
for example, N,Nxe2x80x2-diphenyloxalamide, N-salicylal-Nxe2x80x2-salicyloyl hydrazine, N,Nxe2x80x2-bis(salicyloyl)hydrazine, N,Nxe2x80x2-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine, 3-salicyloylamino-1,2,4-triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,Nxe2x80x2-diacetyladipoyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)oxalyl dihydrazide, N,Nxe2x80x2-bis(salicyloyl)thiopropionyl dihydrazide.
for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl)phosphite, trilauryl phosphite, trioctadecyl phosphite, trimethylphosphine, tri-n-butylphosphine, triphenylphosphine, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl)phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bisisodecyloxypentaerythritol diphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4xe2x80x2-biphenylene diphosphonite, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 2,2xe2x80x2,2xe2x80x3-nitrilo[triethyl-tris(3,3xe2x80x2,5,5xe2x80x3tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite], 2-ethylhexyl (3,3xe2x80x2,5,5xe2x80x2-tetra-tert-butyl-1,1xe2x80x2-biphenyl-2,2xe2x80x2-diyl)phosphite.
Particular preference is given to using the following phosphites:
Tris(2,4-di-tert-butylphenyl)phosphite(Irgafos(copyright)168, Ciba-Geigy), tris(nonylphenyl)phosphite, 
for example N,N-dibenzylhydroxylamine, N,N-diethylhydroxylamine, N,N-dioctylhydroxylamine, N,N-dilaurylhydroxylamine, N,N-ditetradecylhydroxylamine, N,N-dihexadecylhydroxylamine, N,N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,N-dialkylhydroxylamine from hydrogenated tallow fatty amines.
for example N-benzyl alpha-phenyl nitrone, N-ethyl alpha-methyl nitrone, N-octyl alpha-heptyl nitrone, N-lauryl alpha-undecyl nitrone, N-tetradecyl alpha-tridecyl nitrone, N-hexadecyl alpha-pentadecyl nitrone, N-octadecyl alpha-heptadecyl nitrone, N-hexadecyl alpha-heptadecyl nitrone, N-octadecyl alpha-pentadecyl nitrone, N-heptadecyl alpha-heptadecyl nitrone, N-octadecyl alpha-hexadecyl-nitrone, and nitrones derived from N,N-dialkylhydroxylamines prepared from hydrogenated tallow fatty amines.
for example dilauryl thiodiproprionate or distearyl thiodipropionate.
for example esters of xcex2-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakis(xcex2-dodecylmercapto)propionate.
for example copper salts in combination with iodides and/or phosphorus compounds and salts of divalent manganese.
for example melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids, for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate, potassium palmitate, antimony pyrocatecholate or zinc pyrocatecholate.
for example inorganic substances, such as talc, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic acids and their salts, such as 4-tert-butylbenzoic acid, adipic acid, diphenyl acetic acid, sodium succinate or sodium benzoate; and polymeric compounds, for example ionic copolymers (ionomers).
for example calcium carbonate, silicates, glass fibres, glass beads, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibres of other natural products, and synthetic fibres.
for example plasticizers, lubricants, emulsifiers, pigments, rheological additives, catalysts, levelling assistants, optical brighteners, flameproofing agents, antistatic agents, blowing agents.
as described, for example, in U.S. Pat. No. 4,325,863; U.S. Pat. No. 4,338,244; U.S. Pat. No. 5,175,312, U.S. Pat. No. 5,216,052; U.S. Pat. No. 5,252,643; DE-A-4316611; DE-A-4316622; DE-A-4316876; EP-A-0589839 or EP-A-0591102, or 3-[4-(2-acetoxyethoxy)phenyl]-5,7-di-tert-butylbenzofuran-2-one, 5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)phenyl]benzofuran-2-one, 3,3xe2x80x2-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one], 5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one, 3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(3,4-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one, 3-(2,3-dimethylphenyl)-5,7-di-tert-butylbenzofuran-2-one.
The invention provides, furthermore, a process for preparing metathesis polymers, which comprises heating a composition comprising
(xcex1xe2x80x2) dicyclopentadiene or another strained cycloolefin, or dicyclopentadiene in a mixture with another strained cycloolefin, and
(xcex2xe2x80x2) a catalytic amount of at least one compound of the formulae Ia-Ie, in which Me and Me independently of one another are ruthenium or osmium and X, Xxe2x80x2, Y, Yxe2x80x2, L1, L2, L2xe2x80x2, L3, L3xe2x80x2, L4, L5 and L5xe2x80x2, Z, Z1 Z1xe2x80x2, R, Rxe2x80x2 and Rxe2x80x3 are as defined, and isomers of these compounds and, if desired, further additives for polymers
and, if desired, subjecting the obtainable metathesis polymer to a shaping process.
The process of the invention is preferably carried out at a temperature of at least 0xc2x0 C. In particular, the process of the invention is conducted at temperatures from 0xc2x0 to 300xc2x0 C., preferably at from room temperature to 250xc2x0 C., with particular preference from room temperature to 200xc2x0 C. and, with especial preference, at from room temperature to 160xc2x0 C. Following polymerization it may be advantageous to condition the polymers at elevated temperatures, for example from 80 to 200xc2x0 C. To prepare linear polymers the reaction is preferably carried out in dilute solutions.
Polymerization can be associated with shaping processes such as calendering, casting, compression moulding, injection moulding or extrusion, for example. With the process of the invention it is possible to produce materials for the machining production of shaped articles or thermoplastically deformable materials for producing mouldings of all kinds and coatings. Advantageously, shaping and polymerization are connected in solvent-free reactive systems, it being possible to employ processing techniques such as injection moulding, extrusion, polymerization in predetermined forms (possibly under superatmospheric pressure), for example.
The invention also provides the polymers obtainable by the process of the invention.
Of the polymers, preference is given to those containing only carbon and hydrogen.
The polymers prepared by the process of the invention can be homopolymers or copolymers with random distribution of the structural units, graft polymers or block polymers, and crosslinked polymers of this kind. They may have an average molecular weight ({overscore (Mw)}) of, for example, from 500 to 2 million daltons, preferably from 1000 to 1 million daltons (determined by GPC by comparison with polystyrene standards of narrow distribution).
It has surprisingly been found that the polymerization leads in high yields to a polydicyclopentadiene which corresponds to a linear polymer or copolymer having structural units of the formula 
and represents a preferred subject of the invention. A further preferred subject of the invention comprises crosslinked copolymers having structural units of the formula 
which can be prepared by the process of the invention.
The uncrosslinked or linear polymers comprise oligomers and polymers and can contain, for example, from 5 to 5000, advantageously from 10 to 2000, preferably from 20 to 1000, with particular preference from 20 to 500 and, with especial preference, from 20 to 300 structural units. Where the polymers are processed further preference is given to relatively low molecular weights, and in the case of processing to mouldings use is judiciously made of polymers having relatively high molecular weights.
Depending on the nature and amount of the monomers used, the polymers of the invention may have different properties. Some are notable for very high oxygen permeability, excellent dielectric properties (low dielectric constants, low loss factors or tan xcex4 values), good thermal stability (glass transition temperatures above 100xc2x0 C.), good toughnesses (impact and notched impact strength), flexibility and mechanical strengths (fracture resistance), hardness and low water absorption. Others have outstanding optical properties, such as high transparency and low reflective indices, for example. Also deserving of emphasis are the low shrinkage and the excellent surface properties (smoothness, gloss, adhesion). They can therefore be used in a very wide variety of industrial fields.
As coats on the surface of carrier materials, the polymers of the invention are notable for high adhesive strength. In addition, the coated materials are notable for high surface smoothness and gloss. Among the good mechanical properties particular emphasis should be placed on the low shrinkage and high impact strength, but also the thermal stability. Also deserving of mention are the ease of demoulding and the high solvent resistance. The surfaces can be modified further, for example painted or printed, and the high adhesive strengths of the coatings should be mentioned in this case, too.
The polymers obtainable in accordance with the invention are particularly suitable for producing articles of all kinds, such as mouldings for cars, boats, leisure articles, pallets, pipes, sheets, etc.; as insulating materials for producing electrical and electronic components; as implants; as binders for coating materials; as heat-curable compositions for modelling or as adhesives for bonding substrates having low surface energies (Teflon(copyright), polyethylene or polypropylene). The compositions of the invention can also be used to prepare coatings by thermal polymerization, it being possible to use both clear (transparent) and even pigmented compositions. Both white and colour pigments can be used. The production of mouldings by thermoplastic staping processes for consumer articles of all kinds should also be mentioned.
The compositions of the invention are also suitable in particular for producing protective coats. The invention also provides a variant of the process of the invention for producing coated materials, in which the composition of the invention is applied with or without solvent as a film to a carrier, for example by dipping, brushing, flow coating, rolling, knife coating or spin coating techniques, the solvent (if used) is removed, and the film is heated for polymerization. With this process it is possible to modify or protect the surfaces of substrates (corrosion protection).
The present invention provides, furthermore, a coated carrier material wherein a coat of the polymer of the invention has been applied to a substrate.
The present invention likewise provides a coated substrate having a cured film of the polymer of the invention.
Examples of suitable substrates (carrier materials) are those of glass, minerals, ceramics, plastics, wood, semi-metals, metals, metal oxides and metal nitrides. The film thicknesses depend essentially on the desired use and can, for example, be from 0.1 to 1000 xcexcm, preferably from 0.5 to 500 xcexcm and, with particular preference, from 1 to 100 xcexcm. The coated materials are notable for high adhesive strength and good thermal and mechanical properties.
The coated materials of the invention can be prepared by known methods such as brushing, knife coating, flow coating methods such as curtain coating or spin coating.
In the case of coatings, particularly good results are often achieved if the thermal metathesis polymerization is carried out with the additional use of cycloolefins which In addition contain from 1 to three, and preferably one, further double bonds and which in the context of the invention are polycyclic fused ring systems.